Ferroelectric nanomaterials BaTiO3 have uniform size and nano crystal structure morphology. In this paper, LRS-Ⅲ laser Raman/fluorescence spectrometer is used as a measurement instrument for the analysis of solid nanomaterials BaTiO3. Four kinds of non doped ferroelectric nanomaterials are obtained with alkali-heat treatment, labeled pure 1, pure 2, pure 3 and pure as standard sample to be tested; the other two materials doped with different concentrations of EU (europium) elements were labeled as doped 1 and doped 2 to be measured. In this study, we not only compared laser Raman spectra of BaTiO3 with different sintering temperature and time, and gave the corresponding explanation. Meanwhile, we also did a comparative analysis to study the impact of doping on the Raman spectrum. The results show that the Raman spectra of the solid materials with the same composition are similar, and the doping induced changes in the Raman spectra. Finally the correlation coefficient of doping material and none doping material are adopted for further analysis. In conclusion, even if the amount of doping is relatively small, it has a significant impact on the correlation coefficient. Combined with correlation coefficient we can easily determine whether two kinds of substances are similar.